CN112812477B - Filling modified polytetrafluoroethylene and preparation method thereof - Google Patents
Filling modified polytetrafluoroethylene and preparation method thereof Download PDFInfo
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- CN112812477B CN112812477B CN202110177214.6A CN202110177214A CN112812477B CN 112812477 B CN112812477 B CN 112812477B CN 202110177214 A CN202110177214 A CN 202110177214A CN 112812477 B CN112812477 B CN 112812477B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to filling modified polytetrafluoroethylene and a preparation method thereof. The filling modified polytetrafluoroethylene is prepared from resonance mixed powder through curing, mould pressing extrusion, calendaring, extrusion aid removal and stretching and puffing; the resonance mixed powder comprises polytetrafluoroethylene resin, carbon nano tubes, a fluorine-containing silane coupling agent and an extrusion aid. According to the invention, the resonance mixing technology is adopted to replace the traditional high-speed mixing, so that the fibrosis of the polytetrafluoroethylene resin in the mixing process is avoided, and the puffing performance of the polytetrafluoroethylene resin-based material is improved; meanwhile, by adding the fluorine-containing silane coupling agent, the interfacial compatibility of the carbon nano tube and polytetrafluoroethylene is obviously improved, and the dispersion uniformity of the carbon nano tube in the polytetrafluoroethylene is improved; on the basis, the filling modified polytetrafluoroethylene material with high conductivity, high mechanical strength and low density is prepared by combining a stretching and puffing technology.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to filling modified polytetrafluoroethylene and a preparation method thereof.
Background
Polytetrafluoroethylene (PTFE) has excellent properties such as high temperature resistance, corrosion resistance, non-stick, self-lubrication, high dielectric properties, low friction, etc., and can be made into pipes, rods, belts, plates, films, etc., and is widely used in corrosion-resistant pipelines, containers, pumps, valves, radar, high-frequency communication equipment, radio equipment, etc. with high performance requirements.
In recent years, with the wide application of polytetrafluoroethylene materials, in order to meet the demands of the market for polytetrafluoroethylene materials with different properties, more and more filling modified polytetrafluoroethylene materials are developed, and common fillers include carbon nanotubes, glass fibers, metals, metallized oxides, graphite, molybdenum disulfide, carbon fibers, polyimide and the like.
The carbon nano tube has the advantages of high length-diameter ratio, high heat conductivity coefficient, high electric conductivity and the like, and is theoretically an ideal conductive filler for polytetrafluoroethylene filling modification. However, the interface compatibility of the carbon nanotubes and polytetrafluoroethylene is poor, so that the carbon nanotubes are difficult to disperse uniformly in polytetrafluoroethylene, and the conductivity and the mechanical strength of the filling modified material are affected to a certain extent. In addition, the existing filling modified polytetrafluoroethylene material has the problem of poor puffing performance, so that the density of the material after puffing treatment is generally higher.
Disclosure of Invention
In view of the above, the present invention aims to provide a filling modified polytetrafluoroethylene and a preparation method thereof, wherein the filling modified polytetrafluoroethylene has excellent conductivity, high mechanical strength and low density.
The invention provides a filling modified polytetrafluoroethylene, which is prepared by curing, mould pressing extrusion, calendaring, extrusion aid removal and stretching and puffing of resonance mixed powder;
the resonance mixed powder comprises polytetrafluoroethylene resin, carbon nano tubes, a fluorine-containing silane coupling agent and an extrusion aid.
Preferably, the polytetrafluoroethylene resin is dispersed polytetrafluoroethylene resin, suspension polytetrafluoroethylene resin or copolymerization modified polytetrafluoroethylene resin; the carbon nanotubes are functionalized carbon nanotubes; the fluorine-containing silane coupling agent is 1H, 2H-perfluoro decyl triethoxysilane or 1H, 2H-perfluoro octyl trimethoxy silane.
Preferably, the mass ratio of the polytetrafluoroethylene resin to the carbon nano tube to the fluorine-containing silane coupling agent is 1000: (50-100): (1-2).
Preferably, the filling modified polytetrafluoroethylene is prepared by sintering and shaping the product obtained after the stretching and puffing.
The invention provides a preparation method of filled modified polytetrafluoroethylene, which comprises the following steps:
a) Preparing resonance mixed powder; the resonance mixed powder comprises polytetrafluoroethylene resin, carbon nano tubes, a fluorine-containing silane coupling agent and an extrusion aid;
b) And (3) curing, die-pressing extrusion, calendaring, extrusion aid removing and stretching puffing the resonance mixed powder in sequence to obtain the filled modified polytetrafluoroethylene.
Preferably, the resonance mixed powder is prepared according to the following steps:
a1 Directly carrying out resonance mixing on polytetrafluoroethylene resin, a carbon nano tube, a fluorine-containing silane coupling agent and an extrusion assisting agent to obtain resonance mixed powder;
or, a 2) firstly carrying out resonance mixing on the carbon nano tube, the fluorine-containing silane coupling agent and the extrusion assisting agent, and then carrying out continuous resonance mixing on the mixture and the polytetrafluoroethylene resin to obtain resonance mixed powder;
or, a 3) firstly carrying out modification treatment on the carbon nano tube by using a fluorine-containing silane coupling agent to obtain a modified carbon nano tube; and then carrying out resonance mixing on the modified carbon nano tube, polytetrafluoroethylene resin and extrusion aid to obtain resonance mixed powder.
Preferably, in the steps a 1), a 2) and a 3), the vibration acceleration of the resonance mixing is 10 to 100G; the total time of the resonance mixing is 15-45 min.
Preferably, the curing temperature is 40-50 ℃; the curing time is 18-36 h.
Preferably, the die extrusion comprises two processes of die forming and extrusion of a die-formed object;
the pressure of the compression molding is 2-4 MPa; the compression molding time is 2-5 min;
the extrusion pressure of the compression molding product is 8-9 MPa.
Preferably, the temperature of the stretching and puffing is 200-300 ℃; the multiple of the stretching expansion is 3-5 times.
Preferably, the method further comprises: and sintering and shaping the product obtained after stretching and puffing.
Preferably, the temperature of the sintering and shaping is 300-400 ℃; the sintering and shaping time is 1-3 min.
Compared with the prior art, the invention provides the filling modified polytetrafluoroethylene and the preparation method thereof. The filling modified polytetrafluoroethylene is prepared from resonance mixed powder through curing, mould pressing extrusion, calendaring, extrusion aid removal and stretching and puffing; the resonance mixed powder comprises polytetrafluoroethylene resin, carbon nano tubes, a fluorine-containing silane coupling agent and an extrusion aid. The invention adoptsThe resonance mixing technology replaces the traditional high-speed mixing, avoids the fibrosis of the polytetrafluoroethylene resin in the mixing process, and improves the puffing performance of the polytetrafluoroethylene resin-based material; meanwhile, by adding the fluorine-containing silane coupling agent, the interfacial compatibility of the carbon nano tube and polytetrafluoroethylene is obviously improved, and the dispersion uniformity of the carbon nano tube in the polytetrafluoroethylene is improved; on the basis, the filling modified polytetrafluoroethylene material with high conductivity, high mechanical strength and low density is prepared by combining a stretching and puffing technology. Experimental results show that the resistivity of the filled modified polytetrafluoroethylene provided by the invention is 6 multiplied by 10 4 ～7×10 9 Omega cm, tensile strength of 6-14 MPa and density of 0.6-0.8 g/cm 3 。
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a filling modified polytetrafluoroethylene which is prepared by curing, die pressing extrusion, calendaring, extrusion aid removal and stretching and puffing of resonance mixed powder.
The resonance mixed powder comprises polytetrafluoroethylene resin, carbon nano tubes, a fluorine-containing silane coupling agent and an extrusion aid.
The filling modified polytetrafluoroethylene provided by the invention is prepared from resonance mixed powder, and the resonance mixed powder comprises polytetrafluoroethylene resin, carbon nano tubes, fluorine-containing silane coupling agent and extrusion aid. Wherein the polytetrafluoroethylene resin is preferably dispersed polytetrafluoroethylene resin, suspension polytetrafluoroethylene resin or copolymerization modified polytetrafluoroethylene resin, more preferably dispersed polytetrafluoroethylene resin, the brand of the dispersed polytetrafluoroethylene resin is preferably 601X, and the dispersed polytetrafluoroethylene resin of the brand is provided by a large Jin Fuhua worker; the carbon nanotubes are preferably functionalized carbon nanotubes, the functionalized carbon nanotubes are preferably hydroxylated carbon nanotubes or carboxylated carbon nanotubes, the model of the hydroxylated carbon nanotubes is preferably TNDH, the model of the carboxylated carbon nanotubes is preferably TNDC, and the hydroxylated carbon nanotubes and the carboxylated carbon nanotubes of the above models are provided by organic chemistry Co-Ltd; the fluorine-containing silane coupling agent is preferably 1H, 2H-perfluoro decyl triethoxysilane or 1H, 2H-perfluoro octyl trimethoxy silane; the brand of the extrusion aid is preferably isopar K, which is provided by Exxon Mobil; the mass ratio of the polytetrafluoroethylene resin to the carbon nano tube is preferably 1000: (50-100); the mass ratio of the polytetrafluoroethylene resin to the fluorine-containing silane coupling agent is preferably 1000: (1-2); the mass ratio of the tetrafluoroethylene resin to the extrusion aid is preferably 1000: (280-320).
In the filled modified polytetrafluoroethylene provided by the invention, the resonance mixed powder is obtained by resonance mixing of raw materials; the novel paddle-free mixing mode of resonance mixing generates high-intensity vibration through a mechanical resonance principle, so that low-frequency high-intensity waves are generated in the mixed materials to enable the materials to be uniformly mixed. In the invention, the resonance mixed powder is preferably prepared according to the following steps:
a1 Directly carrying out resonance mixing on polytetrafluoroethylene resin, a carbon nano tube, a fluorine-containing silane coupling agent and an extrusion assisting agent to obtain resonance mixed powder;
or, a 2) firstly carrying out resonance mixing on the carbon nano tube, the fluorine-containing silane coupling agent and the extrusion assisting agent, and then carrying out continuous resonance mixing on the mixture and the polytetrafluoroethylene resin to obtain resonance mixed powder;
or, a 3) firstly carrying out modification treatment on the carbon nano tube by using a fluorine-containing silane coupling agent to obtain a modified carbon nano tube; and then carrying out resonance mixing on the modified carbon nano tube, polytetrafluoroethylene resin and extrusion aid to obtain resonance mixed powder.
In the above preparation step provided by the present invention, the vibration acceleration of the resonance mixture is preferably 10 to 100G (1g=9.8 m/s 2 ) More preferably 40G; the total time of the resonance mixing is preferably 15-45 min, and can be 15min or 30minmin or 45min. In step a 2), the time for one resonance mixing is preferably 15min, and the time for continuing the resonance mixing is preferably 30min. In the step a 3), the specific mode of the modification treatment is preferably that the fluorine-containing silane coupling agent and the carbon nano tube are mixed in a solvent, and then the solvent is filtered out and dried to obtain the modified carbon nano tube; the solvent is preferably ethanol; the drying temperature is preferably 100 to 200 ℃, more preferably 150 ℃.
In the invention, the filling modified polytetrafluoroethylene is prepared from the resonance mixed powder through curing, mould pressing extrusion, calendaring, extrusion aid removal and stretching puffing. Wherein the curing temperature is preferably 40-50 ℃, more preferably 45 ℃; the curing time is preferably 18 to 36 hours, more preferably 24 hours; the die extrusion preferably comprises two working procedures of die forming and extrusion of a die-formed object; the pressure of the compression molding is preferably 2-4 MPa, more preferably 3MPa; the time of the compression molding is preferably 2 to 5 minutes, more preferably 3 minutes; the extrusion pressure of the compression molding product is preferably 8-9 MPa; the extrusion aid removing agent is preferably baked; the baking temperature is preferably 180-220 ℃, more preferably 200 ℃; the baking time is preferably 3 to 8min, more preferably 5min; the stretching and puffing temperature is preferably 200-300 ℃, more preferably 250 ℃; the stretching expansion ratio is preferably 3-5 times.
In the invention, the filling modified polytetrafluoroethylene is preferably prepared by sintering and shaping a product obtained after the stretching and puffing; the sintering and shaping temperature is preferably 300-400 ℃, more preferably 350 ℃; the sintering and shaping time is preferably 1-3 min.
The invention also provides a preparation method of the filling modified polytetrafluoroethylene, which comprises the following steps:
a) Preparing resonance mixed powder; the resonance mixed powder comprises polytetrafluoroethylene resin, carbon nano tubes, a fluorine-containing silane coupling agent and an extrusion aid;
b) And (3) curing, die-pressing extrusion, calendaring, extrusion aid removing and stretching puffing the resonance mixed powder in sequence to obtain the filled modified polytetrafluoroethylene.
In the preparation method provided by the invention, resonance mixed powder is prepared firstly, wherein the resonance mixed powder is obtained by resonance mixing of raw materials, and the specific components of the resonance mixed powder comprise polytetrafluoroethylene resin, carbon nano tubes, fluorine-containing silane coupling agent and extrusion aid. Wherein the polytetrafluoroethylene resin is preferably a dispersed polytetrafluoroethylene resin, the brand of the dispersed polytetrafluoroethylene resin is preferably 601X, and the dispersed polytetrafluoroethylene resin with the brand is provided by a large Jin Fuhua worker; the carbon nanotubes are preferably hydroxylated carbon nanotubes, the model of the hydroxylated carbon nanotubes is preferably TNDH, and the hydroxylated carbon nanotubes with the model are provided by organic chemistry Co-Ltd; the fluorine-containing silane coupling agent is preferably 1H, 2H-perfluoro decyl triethoxysilane; the brand of the extrusion aid is preferably isopar K, which is provided by Exxon Mobil; the mass ratio of the polytetrafluoroethylene resin to the carbon nano tube is preferably 1000: (50-100); the mass ratio of the polytetrafluoroethylene resin to the fluorine-containing silane coupling agent is preferably 1000: (1-2); the mass ratio of the tetrafluoroethylene resin to the extrusion aid is preferably 1000: (280-320).
In the preparation method provided by the invention, the resonance mixed powder is preferably prepared according to the following steps:
a1 Directly carrying out resonance mixing on polytetrafluoroethylene resin, a carbon nano tube, a fluorine-containing silane coupling agent and an extrusion assisting agent to obtain resonance mixed powder;
or, a 2) firstly carrying out resonance mixing on the carbon nano tube, the fluorine-containing silane coupling agent and the extrusion assisting agent, and then carrying out continuous resonance mixing on the mixture and the polytetrafluoroethylene resin to obtain resonance mixed powder;
or, a 3) firstly carrying out modification treatment on the carbon nano tube by using a fluorine-containing silane coupling agent to obtain a modified carbon nano tube; and then carrying out resonance mixing on the modified carbon nano tube, polytetrafluoroethylene resin and extrusion aid to obtain resonance mixed powder.
In the above preparation step provided by the present invention, the vibration acceleration of the resonance mixture is preferably 10 to 100G (1g=9.8 m/s 2 ) More preferably 40G; the resonance mixingThe total time of (2) is preferably 15 to 45 minutes, and may be specifically 15 minutes, 30 minutes or 45 minutes. In step a 2), the time for one resonance mixing is preferably 15min, and the time for continuing the resonance mixing is preferably 30min. In the step a 3), the specific mode of the modification treatment is preferably that the fluorine-containing silane coupling agent and the carbon nano tube are mixed in a solvent, and then the solvent is filtered out and dried to obtain the modified carbon nano tube; the solvent is preferably ethanol; the drying temperature is preferably 100 to 200 ℃, more preferably 150 ℃.
In the preparation method provided by the invention, after the resonance mixed powder is obtained, the resonance mixed powder is cured. Wherein the curing is preferably carried out in an oven and the resonating mixed powder is preferably sealed before being placed in the oven; the curing temperature is preferably 40-50 ℃, more preferably 45 ℃; the curing time is preferably 18 to 36 hours, more preferably 24 hours. And after curing is finished, obtaining the cured mixture.
In the preparation method provided by the invention, after the cured mixture is obtained, the cured mixture is molded by compression molding. Wherein the pressure of the compression molding is preferably 2-4 MPa, more preferably 3MPa; the time for the compression molding is preferably 2 to 5 minutes, more preferably 3 minutes. After the compression molding, the obtained compression molded article was extruded. Wherein the extrusion pressure is preferably 8-9 MPa.
In the preparation method provided by the invention, after extrusion of the compression molding object, the compression molding object is rolled to obtain the strip-shaped rolled object. Wherein the thickness of the rolled material is preferably 0.5 to 9mm, more preferably 1 to 3mm, and particularly 1mm or 1.5mm.
In the preparation method provided by the invention, after the rolled material is obtained, the extrusion aid in the rolled material is removed, and the removal mode is preferably baking. Wherein the baking temperature is preferably 180-220 ℃, more preferably 200 ℃; the baking time is preferably 3 to 8 minutes, more preferably 5 minutes.
In the preparation method provided by the invention, the calendared material is stretched and puffed after the extrusion aid is removed. Wherein the temperature of the stretching and puffing is preferably 200-300 ℃, more preferably 250 ℃; the stretching expansion ratio is preferably 3-5 times. And after the stretching and puffing are finished, the filled modified polytetrafluoroethylene provided by the invention is obtained.
In the preparation method provided by the invention, after the stretching and puffing are finished, the obtained stretching and puffing product is preferably sintered and shaped. Wherein the sintering and shaping temperature is preferably 300-400 ℃, more preferably 350 ℃; the sintering and shaping time is preferably 1-3 min.
According to the technical scheme provided by the invention, the traditional high-speed mixing is replaced by adopting a resonance mixing technology, so that the polytetrafluoroethylene resin is prevented from being fibrillated in the mixing process, and the puffing performance of the polytetrafluoroethylene resin-based material is improved; meanwhile, by adding the fluorine-containing silane coupling agent, the interfacial compatibility of the carbon nano tube and polytetrafluoroethylene is obviously improved, and the dispersion uniformity of the carbon nano tube in the polytetrafluoroethylene is improved; on the basis, the filling modified polytetrafluoroethylene material with high conductivity, high mechanical strength and low density is prepared by combining a stretching and puffing technology. Experimental results show that the resistivity of the filled modified polytetrafluoroethylene prepared by the invention is 6 multiplied by 10 4 ～7×10 9 Omega cm, tensile strength of 6-14 MPa and density of 0.6-0.8 g/cm 3 。
For clarity, the following examples are provided in detail.
Example 1
A preparation method of a filling modified polytetrafluoroethylene material comprises the following steps:
50G of hydroxylated carbon nanotube (TNDH, china academy of sciences Chemie Co., ltd.), 1G of 1H, 2H-perfluorodecyl triethoxysilane (Nanjing Netherlands New Material Co., ltd.), 1000G of dispersed polytetrafluoroethylene resin (601X, large Jin Fuhua work) and 280G of extrusion aid (Isopark, exxon Mobil Co.) are added into a resonance mixer and mixed uniformly, and the mixing acceleration is 40G for 30min;
sealing the mixed powder after being mixed evenly, and putting the mixed powder into a baking oven at 45 ℃ for curing for 24 hours; molding the cured mixture for 3min under the pressure of 3MPa to form a cylinder; extruding the compression molding under the pressure of 8 MPa; calendering the extrudate into a 1.5mm thick tape; removing extrusion aid from the rolled material in a baking oven at 200 ℃ for 5min; stretching and puffing for 3 times in a stretching box at 250 ℃; and sintering and shaping for 1min in a sintering box at 350 ℃ to obtain the filling modified polytetrafluoroethylene material.
Example 2
A preparation method of a filling modified polytetrafluoroethylene material comprises the following steps:
1G of 1H, 2H-perfluorodecyl triethoxysilane (Nanjing Netherlands New Material Co., ltd.), 280G of extrusion aid (Isopark, exxon Mobil Co., ltd.), 50G of hydroxylated carbon nanotubes (TNDH, china academy of sciences organic chemistry Co., ltd.) are put into a resonance mixer in advance, mixed at an acceleration of 40G for 15min, and 1000G of dispersed polytetrafluoroethylene resin (601X, jin Fuhua work) are added and mixed continuously for 30min under the same mixed acceleration;
sealing the mixed powder after being mixed evenly, and putting the mixed powder into a baking oven at 45 ℃ for curing for 24 hours; molding the cured mixture for 3min under the pressure of 3MPa to form a cylinder; extruding the compression molding under the pressure of 8 MPa; calendering the extrudate into a 1.5mm thick tape; removing extrusion aid from the rolled material in a baking oven at 200 ℃ for 5min; stretching and puffing for 5 times in a stretching box at 250 ℃; and sintering and shaping for 1min in a sintering box at 350 ℃ to obtain the filling modified polytetrafluoroethylene material.
Example 3
A preparation method of a filling modified polytetrafluoroethylene material comprises the following steps:
firstly, 1g of 1H, 2H-perfluoro decyl triethoxysilane (Nanjing Netherlands New Material Co., ltd.) is dissolved in absolute ethyl alcohol, 50g of carboxylated carbon nanotubes (TNDC, china academy of sciences organic chemistry Co., ltd.) are added and stirred for 30min, and after filtration, the mixture is dried in a blast oven at 150 ℃ to prepare modified carbon nanotubes; then putting the prepared modified carbon nano tube, 1000G of dispersed polytetrafluoroethylene resin (601X, large Jin Fuhua) and 280G of extrusion aid (Isopark, exxon Mobil company) into a resonance mixer, and uniformly mixing, wherein the mixing acceleration is 40G, and the mixing time is 30min;
sealing the mixed powder after being mixed evenly, and putting the mixed powder into a baking oven at 45 ℃ for curing for 24 hours; molding the cured mixture for 3min under the pressure of 3MPa to form a cylinder; extruding the compression molding under the pressure of 8 MPa; calendering the extrudate into a 1.5mm thick tape; removing extrusion aid from the rolled material in a baking oven at 200 ℃ for 5min; stretching and puffing for 5 times in a stretching box at 250 ℃; and sintering and shaping for 3min in a sintering box at 350 ℃ to obtain the filling modified polytetrafluoroethylene material.
Example 4
A preparation method of a filling modified polytetrafluoroethylene material comprises the following steps:
100G of carboxylated carbon nanotubes (TNDC, china academy of sciences Chemie Co., ltd.), 2G of 1H, 2H-perfluorooctyl trimethoxysilane (Nanjing Netherlands New Material Co., ltd.), 1000G of dispersed polytetrafluoroethylene resin (601X, large Jin Fuhua work) and 320G of extrusion aid (Isopark, exxon Mobil Co.) are added into a resonance mixer to be mixed uniformly, the mixing acceleration is 40G, and the mixing time is 30min;
sealing the mixed powder after being mixed evenly, and putting the mixed powder into a baking oven at 45 ℃ for curing for 24 hours; molding the cured mixture for 3min under the pressure of 3MPa to form a cylinder; extruding the compression molding under the pressure of 8 MPa; calendering the extrudate into a 1mm thick tape; removing extrusion aid from the rolled material in a baking oven at 200 ℃ for 5min; stretching and puffing for 5 times in a stretching box at 250 ℃; and sintering and shaping for 1min in a sintering box at 350 ℃ to obtain the filling modified polytetrafluoroethylene material.
Example 5
A preparation method of a filling modified polytetrafluoroethylene material comprises the following steps:
2G of 1H, 2H-perfluoro octyl trimethoxysilane (Nanjing Netherlands New material Co., ltd.), 320G of extrusion aid (Isopark, exxon Mobil Co., ltd.), 100G of carboxylated carbon nanotubes (TNDC, china academy of sciences organic chemistry Co., ltd.) are put into a resonance mixer in advance, mixed with acceleration of 40G for 15min, and 1000G of polytetrafluoroethylene resin (601X, large Jin Fuhua) are added to continue mixing for 30min under the same mixed acceleration;
sealing the mixed powder after being mixed evenly, and putting the mixed powder into a baking oven at 45 ℃ for curing for 24 hours; molding the cured mixture for 3min under the pressure of 3MPa to form a cylinder; extruding the compression molding under the pressure of 8 MPa; calendering the extrudate into a 1mm thick tape; removing extrusion aid from the rolled material in a baking oven at 200 ℃ for 5min; stretching and puffing for 5 times in a stretching box at 250 ℃; and sintering and shaping for 2min in a sintering box at 350 ℃ to obtain the filling modified polytetrafluoroethylene material.
Example 6
A preparation method of a filling modified polytetrafluoroethylene material comprises the following steps:
firstly, 2g of silane coupling agent 1H, 2H-perfluoro octyl trimethoxy silane (Nanjing Netherlands New Material Co., ltd.) is dissolved in absolute ethyl alcohol, 100g of carboxylated carbon nano tube (TNDC, china academy of sciences organic chemistry Co., ltd.) is added and stirred for 30min, and after filtration, the mixture is dried in a blast oven at 150 ℃ to prepare modified carbon nano tube; then putting the prepared modified carbon nano tube, 1000G of dispersed polytetrafluoroethylene resin (601X, large Jin Fuhua work) and 320G of extrusion aid (Isopark, exxon Mobil company) into a resonance mixer, and uniformly mixing, wherein the mixing acceleration is 40G, and the mixing time is 30min;
sealing the mixed powder after being mixed evenly, and putting the mixed powder into a baking oven at 45 ℃ for curing for 24 hours; molding the cured mixture for 3min under the pressure of 3MPa to form a cylinder; extruding the compression molding under the pressure of 8 MPa; calendering the extrudate into a 1mm thick tape; removing extrusion aid from the rolled material in a baking oven at 200 ℃ for 5min; stretching and puffing for 5 times in a stretching box at 250 ℃; and sintering and shaping for 3min in a sintering box at 350 ℃ to obtain the filling modified polytetrafluoroethylene material.
Example 7
A preparation method of a filling modified polytetrafluoroethylene material comprises the following steps:
50G of hydroxylated carbon nanotube (TNDH, china academy of sciences Chemicals Co., ltd.), 1G of 1H, 2H-perfluorodecyl triethoxysilane (Nanjing Netherlands New Material Co., ltd.), 1000G of dispersed polytetrafluoroethylene resin (601X, large Jin Fuhua work) and 280G of extrusion aid (Isopark, exxon Mobil Co.) are put into a resonance mixer and mixed uniformly, and the mixing acceleration is 40G for 30min;
sealing the mixed powder after being mixed evenly, and putting the mixed powder into a baking oven at 45 ℃ for curing for 24 hours; molding the cured mixture for 3min under the pressure of 3MPa to form a cylinder; extruding the compression molding under the pressure of 9MPa; calendering the extrudate into a 1.5mm thick tape; removing extrusion aid from the rolled material in a baking oven at 200 ℃ for 5min; stretching and puffing for 3 times in a stretching box at 250 ℃ to obtain the filling modified polytetrafluoroethylene material.
Index detection
The filling modified polytetrafluoroethylene materials prepared in examples 1 to 7 were examined, and the results are shown in Table 1:
TABLE 1 detection results of filling modified polytetrafluoroethylene Material
| Examples | Resistivity (Ω. Cm) | Tensile Strength (MPa) | Density (g/cm) 3 ) |
| 1 | 5.2×10 8 | 8.8 | 0.66 |
| 2 | 7.6×10 8 | 8.2 | 0.71 |
| 3 | 6.8×10 8 | 7.3 | 0.62 |
| 4 | 8.2×10 4 | 12.1 | 0.68 |
| 5 | 7.6×10 4 | 10.9 | 0.75 |
| 6 | 6.9×10 4 | 13.2 | 0.72 |
| 7 | 6.8×10 9 | 6.8 | 0.62 |
As can be seen from Table 1, the filled modified polytetrafluoroethylene material prepared in the examples of the invention has excellent electrical conductivity, higher mechanical strength and lower density.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A filled modified polytetrafluoroethylene is prepared from resonance mixed powder through curing, mould pressing extrusion, calendaring, extrusion aid removal and stretching and puffing;
the resonance mixed powder comprises polytetrafluoroethylene resin, carbon nano tubes, a fluorine-containing silane coupling agent and an extrusion aid;
the mass ratio of the polytetrafluoroethylene resin to the carbon nano tube to the fluorine-containing silane coupling agent is 1000: (50-100): (1-2); the fluorine-containing silane coupling agent is 1H, 2H-perfluoro decyl triethoxysilane or 1H, 2H-perfluoro octyl trimethoxy silane; the carbon nanotubes are hydroxylated carbon nanotubes or carboxylated carbon nanotubes.
2. The filled modified polytetrafluoroethylene according to claim 1 wherein said polytetrafluoroethylene resin is a dispersed polytetrafluoroethylene resin, a suspension polytetrafluoroethylene resin, or a co-modified polytetrafluoroethylene resin.
3. The filled modified polytetrafluoroethylene according to claim 1 wherein said filled modified polytetrafluoroethylene is formed from said stretched and expanded product by sintering and shaping.
4. A preparation method of filling modified polytetrafluoroethylene comprises the following steps:
a) Preparing resonance mixed powder; the resonance mixed powder comprises polytetrafluoroethylene resin, carbon nano tubes, a fluorine-containing silane coupling agent and an extrusion aid;
the mass ratio of the polytetrafluoroethylene resin to the carbon nano tube to the fluorine-containing silane coupling agent is 1000: (50-100): (1-2); the fluorine-containing silane coupling agent is 1H, 2H-perfluoro decyl triethoxysilane or 1H, 2H-perfluoro octyl trimethoxy silane; the carbon nanotubes are hydroxylated carbon nanotubes or carboxylated carbon nanotubes;
b) And (3) curing, die-pressing extrusion, calendaring, extrusion aid removing and stretching puffing the resonance mixed powder in sequence to obtain the filled modified polytetrafluoroethylene.
5. The preparation method according to claim 4, wherein the resonance mixed powder is prepared by the following steps:
a1 Directly carrying out resonance mixing on polytetrafluoroethylene resin, a carbon nano tube, a fluorine-containing silane coupling agent and an extrusion assisting agent to obtain resonance mixed powder;
or, a 2) firstly carrying out resonance mixing on the carbon nano tube, the fluorine-containing silane coupling agent and the extrusion assisting agent, and then carrying out continuous resonance mixing on the mixture and the polytetrafluoroethylene resin to obtain resonance mixed powder;
or, a 3) firstly carrying out modification treatment on the carbon nano tube by using a fluorine-containing silane coupling agent to obtain a modified carbon nano tube; and then carrying out resonance mixing on the modified carbon nano tube, polytetrafluoroethylene resin and extrusion aid to obtain resonance mixed powder.
6. The method according to claim 5, wherein in steps a 1), a 2) and a 3), the vibration acceleration of the resonance mixing is 10 to 100g; the total time of resonance mixing is 15-45 min.
7. The method according to claim 4, wherein the curing temperature is 40-50 ℃; the curing time is 18-36 h.
8. The method according to claim 4, wherein the extrusion molding comprises two steps of extrusion molding and extrusion molding;
the pressure of compression molding is 2-4 MPa; the compression molding time is 2-5 min;
the extrusion pressure of the compression molding product is 8-9 MPa.
9. The method according to claim 4, wherein the temperature of the stretching and puffing is 200-300 ℃; the stretching expansion multiple is 3-5 times.
10. The method of manufacturing according to claim 4, further comprising: sintering and shaping the product obtained after stretching and puffing;
the temperature of sintering and shaping is 300-400 ℃; the sintering and shaping time is 1-3 min.
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| CN114134606B (en) * | 2021-12-09 | 2023-04-07 | 常州蓝烁环保科技有限公司 | Polytetrafluoroethylene bulked yarn and preparation method of textile prepared from same |
| CN115418739A (en) * | 2022-06-29 | 2022-12-02 | 江苏康隆迪超净科技有限公司 | Polytetrafluoroethylene nanofiber formula and preparation method thereof |
| CN116355337B (en) * | 2023-06-01 | 2023-08-08 | 山东美氟科技股份有限公司 | Fluorine-containing polymer-carbon nano tube modified polytetrafluoroethylene and preparation process thereof |
| CN116622175A (en) * | 2023-07-25 | 2023-08-22 | 无锡市凯利健密封科技有限公司 | High-durability polytetrafluoroethylene sealing gasket and preparation method thereof |
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